JP7003764B2 - Reactive block copolymer - Google Patents

Description

The present invention relates to a urea-based or urethane-based novel reactive block copolymer and a method for producing the same, which is useful as a highly elastic recovery material for flexible device applications in the field of electronic information materials. Furthermore, it relates to materials that can be horizontally expanded to various uses such as automobiles, building materials, and life sciences, and their manufacturing methods.

In recent years, LCD (liquid crystal display) terminals that are portable and can be used outdoors have become widespread, and smartphones, mobile terminals such as PNDs (personal navigation devices), and wearable displays such as Google Glass have become popular. Take as an example.
With the practical application of organic EL displays, further weight reduction is required, and a method of switching a part of a member from glass or thin film glass to plastic is adopted. However, while thin film glass has excellent heat resistance, it is extremely fragile, and plastics (particularly PET, PC, PMMA, cycloolefin polymers, etc.) are lightweight and highly transparent, but they are impact resistant and scratch resistant. Since mechanical properties such as sex may be poor, the development of new functional plastics has been required.

Patent Document 1 discloses a coating agent for a glass substrate having excellent scratch resistance and excellent adhesion to glass and anti-scattering property (paragraph 0019). However, although the obtained glass coating layer has excellent scratch resistance and shatterproof properties, it is insufficient when used in recent smartphones and wearable displays.
On the other hand, Patent Document 2 is a new product having high hardness and toughness useful for various rolls such as calendar rolls used for papermaking, textiles, magnetic tapes, casters and other general molding resins, and excellent heat resistance. Polyurea resin is disclosed (paragraph 0001). However, the technique relates to a general molding resin used by injecting it into a mold, and is not intended to be applied to a film-shaped mobile terminal or the like in terms of handling and the like.
Further, Patent Document 3 states that it can be obtained by heat treatment at a low temperature, has good adhesion to a substrate and a sealing material, has improved tin plating resistance, and further has a warp. Has excellent heat resistance, solder flux resistance, solvent resistance, chemical resistance, bending resistance, and electrical characteristics, and can be applied well on substrates such as flexible wiring boards. A polyimide siloxane-based insulating film composition for forming an insulating film such as a component is disclosed. However, this technology is intended for application to flexible wiring boards, and does not take into consideration the transparency required for display applications.

Japanese Unexamined Patent Publication No. 2006-290696 Japanese Unexamined Patent Publication No. 5-194695 Japanese Unexamined Patent Publication No. 2004-231757

An object of the present invention is to provide a novel reactive block copolymer having a urea bond or a urethane bond in the molecule, which has excellent properties of transparency, heat resistance and mechanical properties, and a method for producing the same. be.

Furthermore, since the novel reactive block copolymer of the present invention has a polymerizable functional group whose terminal group can be radically cured by irradiation with active energy rays, it can be easily cured by irradiation with active energy rays such as ultraviolet rays or electron beams. Can be obtained.

As a result of intensive research to achieve the above object, the present inventor
An aliphatic diisocyanate compound <A> having a cyclic structure in the molecule and an alternating copolymer 1 obtained by a double addition reaction of a diamine compound <B>.
An aliphatic diisocyanate compound <A> having a cyclic structure in the molecule and an alternating copolymer 2 which is a heavy addition of a specific diamine compound <C ¹ > or a diol compound <C ² > were further added. A reactive block copolymer and a reactive block copolymer to which a compound <E> having a group that can be added to both terminal groups of the block copolymer and having a polymerizable functional group that can be radically cured by irradiation with active energy rays is added. The manufacturing method was found, and the present invention was completed.
Examples of aspects of the present invention are shown below.

[1] It contains a repeating unit represented by the formula (3), which is a double addition copolymer of the following alternate copolymer 1 and the following alternate copolymer 2, and has a weight average molecular weight of 50 to 1,000,000. Yes, at both ends of the block copolymer (P) whose ends are either -NH ₂ , -OH or -NCO.
A reactive block to which a compound <E> having a group that can be added to both terminal groups of the block copolymer (P) and having a polymerizable functional group that can be radically cured by irradiation with active energy rays is added. Block Polymer (Q). (Hereinafter, the "reactive block copolymer" is also described with the symbol "(Q)".)
-[(Alternate copolymer 1)-(Alternate copolymer 2)-]-Formula (3)
Alternating copolymer 1:
It is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <B>, and is of the formula (1).
-[(A)-(B)-]-Equation (1)
Polyurea-based alternating copolymer containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NH ₂ or -NCO at both ends;
Alternating copolymer 2:
It is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <C ¹ >, and is of the formula (2-1).
-[(A)-(C ¹ )-]-Equation (2-1)
Polyurea-based alternating copolymer 2-1 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -NH ₂ at both ends.
And a polyaddition copolymer of the diisocyanate compound <A> and the diol compound <C ² >, of the formula (2-2).
-[(A)-(C ² )-]-Equation (2-2)
Polyurethane-based alternating copolymer 2-2 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -OH at both ends.
At least one alternating copolymer selected from;
(In the formula (A), at least one of the aliphatic isocyanate structural units having an independent cyclic structure in the molecule;
(B) is at least one structural unit independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
(C ¹ ) is at least one structural unit selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton.
However, when both ends of the alternate copolymer 1 are -NCO, both ends of the alternate copolymer 2 are -NH ₂ or -OH;
When both ends of the alternate copolymer 1 are -NH ₂ , both ends of the alternate copolymer 2 are -NCO. )

[2] The reactive block copolymer (Q) according to the above [1], wherein the polymerizable functional group capable of radical curing by irradiation with active energy rays is a (meth) acryloyl group.

[3] Both ends of the block copolymer (P) are independently -NH ₂ or -OH;
The group that can be added to both terminal groups of the block copolymer (P) of compound <E> is -NCO, and the polymerizable functional group that can be radically cured by irradiation with active energy rays is a (meth) acryloyl group. The reactive block copolymer (Q) according to the above [1], which is characterized by the above.

[4] Both ends of the block copolymer (P) are -NCO;
The groups that can be added to both terminal groups of the block copolymer (P) of compound <E> are -NH ₂ groups, -COOH or -OH, and radical curing by irradiation with active energy rays is possible. The reactive block copolymer (Q) according to the above [1], wherein the polymerizable functional group is a (meth) acryloyl group.

[5] The item according to any one of [1] to [4] above, wherein both ends of the alternate copolymer 1 are -NCO and both ends of the alternate copolymer 2 are -NH ₂ or -OH. Reactive block copolymer (Q).

[6] The reactivity according to any one of [1] to [4] above, wherein both ends of the alternate copolymer 1 are -NH ₂ and both ends of the alternate copolymer 2 are -NCO. Block copolymer (Q).

[7] The reactive block copolymer (Q) according to any one of [1] to [6] above, wherein the alternate copolymer 2 is a polyurea-based alternate copolymer 2-1.

[8] The reactive block copolymer (Q) according to any one of the above [1] to [6], wherein the alternate copolymer 2 is a polyurethane-based alternate copolymer 2-2.

[9] The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X).
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or linear or branched alkyl having 1 to 7 carbon atoms.
X is an independently linear or branched alkylene having 1 to 7 carbon atoms.
Y is independently oxygen, sulfur, a linear or branched alkylene with 1-7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- , respectively.
The reactive block copolymer (Q) according to any one of the above [1] to [8].

The reactive block copolymer (Q) obtained in the present invention is soluble in a general-purpose organic solvent, and has the effects of being excellent in transparency, heat resistance, film forming property, and flexibility.

Hereinafter, the reactive block copolymer (Q) and the method for producing the reactive block copolymer (Q) according to the present invention and their uses will be described in detail.

The reactive block copolymer (Q) of the present invention contains a repeating unit represented by the formula (3), which is a double addition copolymer of the following alternating copolymer 1 and the following alternating copolymer 2. At both ends of the block copolymer (P), which has a weight average molecular weight of 5,000 to 500,000 and ends in either -NH ₂ or -NCO.
A reactive block to which a compound <E> having a group that can be added to both terminal groups of the block copolymer (P) and having a polymerizable functional group that can be radically cured by irradiation with active energy rays is added. It is a copolymer (Q).
-[(Alternate copolymer 1)-(Alternate copolymer 2)-]-Formula (3)
However, when both ends of the alternate copolymer 1 are -NCO, both ends of the alternate copolymer 2 are -NH ₂ or -OH;
When both ends of the alternate copolymer 1 are -NH ₂ , both ends of the alternate copolymer 2 are -NCO.
The elements constituting this reactive block copolymer (Q) will be sequentially described below.

1 Alternate copolymer 1
The alternating copolymer 1 is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <B>.
Equation (1)
-[(A)-(B)-]-Equation (1)
It is a polyurea-based alternating copolymer containing a repeating unit represented by the above, having a weight average molecular weight of 5 to 300,000, and having -NH ₂ or -NCO at both ends.
((A) in the formula is selected from at least one of the aliphatic diisocyanate structural units having a cyclic structure in the molecule, and (B) is independently selected from the aromatic diamine and the structural unit of the aromatic diamine having an ether bond, respectively. It is at least one kind.)

The alternating copolymer 1 is obtained by double-adding the diisocyanate compound <A> and the diamine compound <B>. The diisocyanate compound <A> and the diamine compound <B> correspond to the structural unit (A) and the structural unit (B) in the alternating copolymer 1, respectively. The binding site between the structural units (A) and (B) is a urea structure (-NH-CO-NH-).

The structural unit of the alternate copolymer 1 is considered to be a structural unit (hard segment) that contributes to rigidity and heat resistance in the physical properties of the reactive block copolymer (Q).

1.1 Diisocyanate compound <A>
The diisocyanate compound <A> that can be used in the present invention is not particularly limited as long as it is an aliphatic diisocyanate compound having a cyclic structure in the molecule, but specific examples thereof include the following formulas (I) to (I). Examples thereof include a diisocyanate compound represented by X).

The aliphatic diisocyanate of the present invention is a compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to a linear or branched aliphatic hydrocarbon or a carbon of an aliphatic ring. ..

In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or linear or branched alkyl having 1 to 7 carbon atoms.
X is an independently linear or branched alkylene having 1 to 7 carbon atoms.
Y is independently oxygen, sulfur, a linear or branched alkylene having 1 to 7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- .

Among the above specific examples, the diisocyanate compounds represented by the formulas (V), (VI) and (VIII) are preferable because of their high solubility in a solvent. Further, when high transparency and heat resistance are required, the diisocyanate compounds represented by the formulas (V) and (VI) can be particularly preferably used.

Further, the diisocyanate compound <A> that can be used in the present invention is not particularly limited as long as it is an aliphatic diisocyanate compound having a cyclic structure in the molecule, and is disclosed in, for example, Japanese Patent Application Laid-Open No. 2016-199694. Examples thereof include compounds that have been used.

An aliphatic diisocyanate having a cyclic structure in the molecule; isophorone diisocyanate, (bicyclo [2.2.1] heptane-2,5-diyl) bismethylene diisocyanate, (bicyclo [2.2.1] heptane-2,6- Diyl) Bismethylene diisocyanate, 2β, 5α-bis (isocyanate) norbornan, 2β, 5β-bis (isocyanate) norbornan, 2β, 6α-bis (isocyanate) norbornan, 2β, 6β-bis (isocyanate) norbornan, 2,6- Di (isocyanatemethyl) furan, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, dicyclohexylmethanediisocyanate, 4,4-isopropylidenebis (cyclohexylisocyanate), cyclohexane Diisocyanate, methylcyclohexanediisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethanediisocyanate, bis (4-isocyanate-n-butylidene) pentaerythritol, dimerate diisocyanate, 3,8-bis (isocyanatemethyl) Tricyclodecane, 3,9-bis (isocyanatemethyl) tricyclodecane, 4,8-bis (isocyanatemethyl) tricyclodecane, 4,9-bis (isocyanatemethyl) tricyclodecane, 1,5-diisocyanatedecalin, 2,7-Diisocyanate decalinate, 1,4-diisocyanate decalinate, 2,6-diisocyanate decalinate, dicyclohexylsulfide-4,4'-diisocyanate, tricyclothiaoctanediisocyanate

As the diisocyanate compound described above, only one kind may be used, or two or more kinds may be mixed and used.

1.2 Diamine compound <B>
The diamine compound <B> that can be used in the present invention is particularly limited as long as it is a diamine compound that is independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton. It's not a thing. For example, a diamine compound disclosed in Japanese Patent Application Laid-Open No. 2014-56921 can be used.

The "aliphatic diamine having a cyclic skeleton" is a linear or branched aliphatic hydrocarbon in which an amino group is directly bonded, has a cyclic structure in the molecule, and has an amino group in the molecule. It is a compound having two. The "aromatic diamine" is a compound having two amino groups in the molecule, in which an amino group is directly bonded to the carbon of the aromatic ring.

In particular, the diamine compound <B> that can be used to impart high heat resistance is a diamine compound selected from aromatic diamines, aromatic diamines having an ether bond, and aliphatic diamines having a cyclic skeleton. Specific examples include 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-. Diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, m-phenylenediamine, p-phenylenediamine, m-xylylene diamine, p-xylylene diamine, 2,2'-diaminodiphenylpropane, benzidine, 1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, bis [4- (4-aminobenzyl) Phenyl] methane, 1,1-bis [4- (4-aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] 4-methylcyclohexane, 1,1-bis [4 -(4-Aminobenzyl) phenyl] cyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] -4-methylcyclohexane, 1,1-bis [4- (4-aminobenzyl) phenyl] methane 4,4'-bis (4-aminophenoxy) biphenyl, 1.6-bis (4-((4-aminophenyl) methyl) phenyl) hexane, α, α'-bis (4-aminophenyl) -1 , 4-diisopropylbenzene, 1,4-diaminocyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylmethane and the like.

Among the above specific examples, 4,4'-diaminodiphenylmethane, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (Aminomethyl) cyclohexane and 4,4'-diaminodicyclohexylmethane are preferable in terms of heat resistance and mechanical properties, and 4,4'-diaminodiphenylmethane and 2,2-bis [4- (4-aminophenoxy) phenyl]. Propane can be used particularly preferably.

In particular, examples of the diamine compound <B> that can be used to impart high heat resistance include aliphatic diamines having a cyclic skeleton represented by the formulas (XIII-1) and (XIII-2).

For example, aliphatic diamines having a cyclic skeleton represented by the formulas (XIV-1) to (XIV-3) can be mentioned.

For example, aromatic diamines represented by the formulas (XV-1) to (XV-5) can be mentioned.

For example, aromatic diamines represented by formulas (XVI-1) to (XVI-12), formulas (XVI-20) to (XVI-30), and formulas (XVI-13) to (XVI-19). Examples thereof include aromatic diamines having an ether bond.

For example, aromatic diamines represented by the formulas (XVII-1) to (XVII-4) and aromatic diamines having an ether bond represented by the formulas (XVII-5) and (XVII-6) can be mentioned.

For example, aromatic diamines represented by the formulas (XVIII-1) to (XVIII-7) and aromatic diamines having an ether bond represented by the formulas (XVIII-8) to (XVIII-11) can be mentioned.

The diamine compound <B> of the present invention is not limited to the diamine of the present specification, and various other forms of diamine can be used as long as the object of the present invention is achieved. Further, the diamine compound described above may be used alone or in combination of two or more.

2 Alternating copolymer 2
The alternating copolymer 2 is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <C ¹ >.
Equation (2-1)
-[(A)-(C ¹ )-]-Equation (2-1)
Polyurea-based alternating copolymer 2-1 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -NH ₂ at both ends.
And a polyaddition copolymer of the diisocyanate compound <A> and the diol compound <C ² >, of the formula (2-2).
-[(A)-(C ² )-]-Equation (2-2)
Polyurethane-based alternating copolymer 2-2 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -OH at both ends.
At least one alternating copolymer selected from.
(In the formula (A), at least one of the aliphatic isocyanate structural units having an independent cyclic structure in the molecule;
(C ¹ ) is at least one structural unit selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from linear aliphatic diols, aliphatic diols having an ether bond and diols having a siloxane skeleton. )

As the alternating copolymer 2, either the polyurea-based alternating copolymer 2-1 represented by the formula (2-1) or the polyurethane-based alternating copolymer 2-2 represented by the formula (2-2) can be used. It may be used or both may be used together.

The alternating copolymer 2 is obtained by double-adding the diisocyanate compound <A> and the diamine compound <C ¹ > or the diol compound <C ² >. The diisocyanate compound <A>, the diamine compound <C ¹ > and the diol compound <C ² > correspond to the structural unit (A), the structural unit (C ¹ ) and (C ² ) in the alternating copolymer 2, respectively. The binding site between the structural units (A) and (C ¹ ) is a urea structure (-NH-CO-NH-), and the binding site between the structural units (A) and (C ² ) is a urethane structure (-NH-CO). -O-).

The structural unit of the alternate copolymer 2 is considered to be a structural unit (soft segment) that contributes to solubility, flexibility, and extensibility in the physical properties of the reactive block copolymer (Q).

2.1 Diisocyanate compound <A>
The diisocyanate compound <A> that can be used in the alternate copolymer 2 is the same as the diisocyanate compound <A> used in the alternate copolymer 1.

2.2 Diamine compound <C ¹ > and diol compound <C ² >
As the diamine compound <C ¹ > or the diol compound <C ² > used for the alternate copolymer 2, either of them may be selected, and polyurea-based alternating is performed by double-adding each of them with the diisocyanate compound <A>. A copolymer 2-1 and a polyurethane-based alternating copolymer 2-2 can be obtained. Further, the diamine compound <C ¹ > and the diol compound <C ² > may be used in combination. In this case, the alternate copolymer 2 is a copolymer containing a urea structure and a urethane structure at the same time.

2.2.1 Diamine compound <C ¹ >
The diamine compound <C ¹ > is at least one selected from a linear aliphatic diamine compound, an aliphatic diamine compound having an ether bond, and a diamine compound having a siloxane skeleton. For example, the compound disclosed in Japanese Patent Application Laid-Open No. 2014-56921 can be used.

The "aliphatic diamine" of the present invention is a compound having two amino groups in the molecule, in which an amino group is directly bonded to the carbon of a linear or branched aliphatic hydrocarbon or an aliphatic ring. Is.

In particular, the diamine compound <B> that can be used to impart high transparency is a diamine compound selected from linear aliphatic diamines, aliphatic diamines having an ether bond, and diamines having a siloxane skeleton. Specific examples include 1,4-diaminobutane, 1,6-diaminohexane, 1,12-diaminododecane, 1,2-bis (2-aminoethoxy) ethane, diethylene glycolbis (3-aminopropyl) ether, 1, Examples thereof include 4-butanediol bis (3-aminopropyl) ether, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane, and a diamine compound having a siloxane skeleton represented by the following formula (XI).

In the formula, R ₅ and R ₆ are independently alkyl or phenyl having 1 to 3 carbon atoms, and R ₇
Is independently methylene, phenylene or phenylene in which at least one hydrogen is replaced with an alkyl, x is independently an integer of 1 to 6, and y is an integer of 0 to 70.

Among the above specific examples, 1,12-diaminododecane, diethylene glycol bis (3-aminopropyl) ether, and a diamine compound having a siloxane skeleton of the formula (XI) are preferable in terms of transparency and mechanical properties, and diethylene glycol bis (3). -Aminopropyl) ether, a diamine compound having a siloxane skeleton of the formula (XI) can be particularly preferably used.

In particular, examples of the diamine compound <B> that can be used to impart high transparency include linear aliphatic diamines represented by the formulas (XII-1) to (XII-3) and the formula (XII-). 4) Examples thereof include aliphatic diamines having an ether bond represented by (XII-8).

In the formula (XII-7), n is an integer of 1 to 30, and in the formula (XII-8), a is 0 to 20, b is 0 to 70, and c is 1 to 90.

Examples of the aliphatic diamine having an ether bond represented by the formula (XII-8) include trade names: Jeffamine D-230 (a = 0, b = 0, c = 2) manufactured by Mitsui Kagaku Fine Co., Ltd. ~ 3), D-400 (a = 0, b = 0, c = 5-6), D-2000 (a = 0, b = 0, c = about 33), D-4000, etc. Jeffermin D series Jeffermin ED-600 (b = 9.0, a + c = 3.6), ED-900 (b = 12.0, a + c = 3.6), ED-2003 (b = 38.7, a + c = 6) .0) et al. Jeffamine ED series; etc. can be used.

2.2.2 Diol compound <C ² >
The diol compound <C ² > is at least one selected from a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton. As the diol compound <C ² >, a compound having a structure in which the two -NH ₂ in the above diamine compound <C ¹ > is replaced with -OH can be used.

Specific examples of the diol compound <C ² > are given below, but the diol compound <C 2> is not limited to these examples.
Examples of the alkylene diol or polyoxyalkylene diol compound include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, tetramethylene glycol and polytetramethylene glycol. 1,3-Butanediol, 1,4-Butanediol, 2,3-Butanediol, 1,5-Pentanediol, 1,7-Heptanediol, 1,6-Hexanediol, Hexylene glycol, Neopentyl glycol, Poly1,2-butylene glycol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol 1,4-cyclohexanedimethanol, methylpentanediol-modified polytetramethylene Glycol, propylene glycol modified polytetramethylene glycol, ethylene glycol-propylene glycol block copolymer, ethylene glycol-tetramethylene glycol copolymer, 2-methyl-1,8-octanediol, 1,9-nonanediol, 3-methyl-1 , 5-Pentylene diol, Silaplane FM4411 (manufactured by JNC Co., Ltd., double-ended hydroxyl-modified silicon compound, Mn = 1000), Silaplane FM4421 (manufactured by JNC Co., Ltd., both-terminal hydroxyl-modified silicon compound, Mn = 5000), Examples thereof include Cyraplane FM4425 (manufactured by JNC Co., Ltd., both-terminal hydroxyl-modified silicon compound, Mn = 10000). These may be used alone or in combination of two or more.

3 Reactive block copolymer (Q)
The reactive block copolymer (Q) of the present invention contains a repeating unit represented by the formula (3), which is a polyaddition copolymer of the above-mentioned alternating copolymer 1 and the alternating copolymer 2. At both ends of the block copolymer (P), which has a weight average molecular weight of 50 to 1,000,000 and ends with either -NH ₂ -OH or -NCO.
A reactive block to which a compound <E> having a group that can be added to both terminal groups of the block copolymer (P) and having a polymerizable functional group that can be radically cured by irradiation with active energy rays is added. It is a copolymer (Q).
-[(Alternate copolymer 1)-(Alternate copolymer 2)]-Formula (3)
The alternating copolymer 1 and the alternating copolymer 2 are bonded via a urea bond or a urethane bond.

In the reactive block copolymer (Q) of the present invention, when both ends of the alternate copolymer 1 are -NCO, both ends of the alternate copolymer 2 are -NH ₂ or -OH; alternate co-polymers. When both ends of the polymer 1 are -NH ₂ , both ends of the alternate copolymer 2 are -NCO. Both of these terminal groups undergo a double addition reaction to form a urea bond or a urethane bond, resulting in the reactive block copolymer (Q) of the present invention.

When both ends of the block copolymer (P) are independently -NH ₂ or -OH,
The group that can be added to both terminal groups of the block copolymer (P) of compound <E> is -NCO, and the polymerizable functional group that can be radically cured by irradiation with active energy rays is a (meth) acryloyl group. The compound <E> is reacted to form a urea bond or a urethane bond, and the reactive block copolymer (Q) of the present invention is obtained.

When both ends of the block copolymer (P) are -NCO,
The groups that can be added to both terminal groups of the block copolymer (P) of compound <E> are -NH ₂ groups, -COOH or -OH, and radical curing by irradiation with active energy rays is possible. The polymerizable functional group reacts with the compound <E>, which is a (meth) acryloyl group, to form a urea bond, and the reactive block copolymer (Q) of the present invention is obtained.

The structure of the reactive block copolymer (Q) is schematically represented by the following formula (4).
(E)-(block copolymer (P))-(E) formula (4)
The reactive block copolymer (Q) is obtained by reacting compound <E> with both terminal groups of the block copolymer (P). Compound <E> corresponds to the structural unit (E) at both ends of the block copolymer (P) in the formula. The bond site between the block copolymer (P) and the structural unit (E) has a urea structure (-NH-CO-NH-), a urethane structure (-NH-CO-O-), and a structure in which the left and right directions are reversed. (Including) or -CO-O-CO-NH-structure (including the structure in which the left and right are reversed).

4 Method for producing the reactive block copolymer (Q) Hereinafter, the method for producing the block copolymer (P) will be collectively described from the stage of producing the alternate copolymer 1 and the alternate copolymer 2.

In the polyaddition reaction and the polycondensation reaction, by changing the charging ratio (molar ratio) of the two types of monomers, an alternating copolymer having a terminal group corresponding to the monomer structure can be obtained, and the molecular weight can be arbitrarily obtained. Can also be controlled. This is Billmeyer. F. W. Step-Reaction (Condensation) Polymerization. In Textbook of Composer Science; John Wiley &Sons; Singapore, 1994; pp35-39. It is described in.

Based on the above theory, when both ends of the alternate copolymer 1 constituting the block copolymer (P) are -NCO, both ends of the alternate copolymer 2 need to be -NH ₂ or -OH. On the contrary, when both ends of the alternate copolymer 1 are -NH ₂ , both ends of the alternate copolymer 2 need to be -NCO.

For example, in the case of producing a polymer in which both ends of the alternate copolymer 1 are −NCO, the diisocyanate compound <A> is added in the step (step 1) of double-adding the diisocyanate compound <A> and the diamine compound <B>. The number of moles of the diamine compound <B> may be larger than the number of moles of the diamine compound <B>. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, the number of moles of each is 1.06 ≦ n1 / n2 ≦ 1.9. It is preferable to adjust. In this way, the weight average molecular weight of the alternating copolymer 1 having -NCO at both ends can be adjusted in the range of 500,000 to 300,000.

In that case, since both ends of the alternate copolymer 2 are -NH ₂ or -OH, a diisocyanate compound <A> and a diamine compound <C ¹ > or a diol compound <C ² > are produced. In the step of polymerizing (step 2), the number of moles of the diamine compound <C ¹ > or the diol compound <C ² > may be larger than the number of moles of the diisocyanate compound <A>. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <C ¹ > or the diol compound <C ² > is n2, the number of moles of each is 1.06 ≦ n2 / n1 ≦ 1. It is preferable to adjust so that the relationship is 9. In this way, the weight average molecular weight of the alternating copolymer 2 having -NH ₂ at both ends can be adjusted in the range of 500,000 to 300,000.

Further, for example, in the case of producing a polymer in which both ends of the alternate copolymer 1 are −NH ₂ , the diamine compound is added in a step (step 1) in which the diisocyanate compound <A> and the diamine compound <B> are double-added. The number of moles of <B> may be larger than the number of moles of the diisocyanate compound <A>. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <B> is n2, the number of moles of each is 1.06 ≦ n2 / n1 ≦ 1.9. It is preferable to adjust. In this way, the weight average molecular weight of the alternating copolymer 1 having -NH ₂ at both ends can be adjusted in the range of 500,000 to 300,000.

In that case, since both ends of the alternate copolymer 2 are -NCO, the diamine compound <A> and the diamine compound <C ¹ > or the diol compound <C ² > are polymerized. In (step 2), the number of moles of the diisocyanate compound <A> may be larger than the number of moles of the diamine compound <C ¹ > or the diol compound <C ² >. For example, when the number of moles of the diisocyanate compound <A> is n1 and the number of moles of the diamine compound <C ¹ > or the diol compound <C ² > is n2, the number of moles of each is 1.06 ≦ n1 / n2 ≦ 1. It is preferable to adjust so that the relationship is 9. In this way, the weight average molecular weight of the alternating copolymer 2 having -NCO at both ends can be adjusted in the range of 500,000 to 300,000.

Next, a method for producing the block copolymer (P) will be described. As the block copolymer (P), a stepwise production method (hereinafter referred to as a stepwise polymerization method) exemplified in the following (i) to (v) is adopted.
(I) The block copolymer (P) is produced by introducing the alternate copolymer 1 obtained in step 1 and the alternate copolymer 2 obtained in step 2 into the same reaction vessel and performing a double addition reaction. Method (ii) A method for producing a block copolymer (P) by introducing the alternate copolymer 1 obtained in step 1 into a reaction vessel and then carrying out step 2 (iii) in step 2. A method for producing a block copolymer (P) by introducing the obtained alternate copolymer 2 into a reaction vessel and then carrying out step 1. (iv) After carrying out step 1 in the same container, Method for Producing Block Polymer (P) by Continuely Carrying Step 2 (v) After carrying out Step 2 in the same container, Continue Carrying Step 1 to Produce Block Polymer (P). Although the block copolymer (P) can be obtained by any of the step polymerization methods, a plurality of one or more step polymerization methods may be combined or selected in order to obtain the desired properties. A method of repeating the step polymerization method a plurality of times may be adopted.

Next, the structural change of the reactive block copolymer (P) will be described. Since the molecular weights of the alternate copolymers 1 and 2 can be arbitrarily controlled in the steps 1 and 2, block copolymers (P) having different block chain lengths can be obtained. The molecular weight of the block copolymer (P) can also be controlled by changing the molar ratio of the alternate copolymer 1 and the alternate copolymer 2 obtained in the steps 1 and 2. The weight average molecular weight of the block copolymer (P) is preferably in the range of 5,000 to 1,000,000, more preferably 5,000 to 300,000.

Next, a method for producing a reactive block copolymer (Q) in which radically polymerizable functional groups are imparted to the terminal groups of the block copolymer (P) by irradiation with active energy rays will be described.
After producing the block copolymer (P) obtained by the method described above, the number of groups that can be added to both end groups of the block copolymer (P) is -NH ₂ in the same container. , -COOH, -OH, or -NCO, and the polymerizable functional group capable of radical curing by irradiation with active energy rays is a (meth) acryloyl group, and the reaction is carried out by introducing the compound <E>. This will produce a reactive block copolymer (Q).

5. Other diisocyanate compounds <D>
In the reactive block copolymer (Q) of the present invention, both the alternate copolymer 1 and the alternate copolymer 2 are structural units of the diisocyanate compound <A>, that is, an aliphatic isocyanate structural unit (A) having a cyclic structure. However, a part of the diisocyanate compound <A> may be used in place of another diisocyanate compound <D> (structural unit (D)). The other diisocyanate compound may be contained in a part of the alternate copolymer 1, may be contained in a part of the alternate copolymer 2, and is a portion to which the respective alternate copolymers are bonded. It may be sandwiched between the structures of the above, or may be bonded to the end of the block copolymer (P).

The other diisocyanate compounds are not particularly limited as long as they are compounds other than the diisocyanate compound <A> and have two diisocyanate groups in the molecule. As specific examples of other diisocyanate compounds, the following compounds can be used.

Preferred specific examples of other diisocyanate compounds include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, and trioxyethylene diisocyanate. , 2,4'-toluene diisocyanate (2,4'-TDI), 2,6'-toluene diisocyanate (2,6'-TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate, Examples thereof include 1,5-naphthalenediocyanate.

Further, as other diisocyanate compounds, for example, aliphatic diisocyanates, aromatic diisocyanates, sulfur-containing aliphatic diisocyanates, aliphatic sulfide-based diisocyanates, aromatic sulfide-based diisocyanates and aliphatics disclosed in Japanese Patent Application Laid-Open No. 2016-199694. Examples thereof include sulfone-based diisocyanates, aromatic sulfone-based diisocyanates, sulfonic acid ester-based diisocyanates, aromatic sulfonic acid amide-based diisocyanates, and sulfur-containing heterocyclic diisocyanates. Specific examples of these diisocyanate compounds include the following compounds.

The aromatic diisocyanate referred to in the present invention is a compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to the carbon of the aromatic ring. The heterocyclic diisocyanate of the present invention is a compound having two isocyanate groups in the molecule, in which an isocyanate group is directly bonded to the carbon of the heterocycle containing a hetero atom.

Further, the sulfide-based diisocyanate, the sulfone-based diisocyanate, the sulfonic acid ester-based diisocyanate, and the sulfonic acid amide-based diisocyanate of the present invention each have a structure of sulfide, sulfone, sulfonic acid ester, and sulfonic acid amide in the molecule, and are molecules. It is a compound having two isocyanate groups inside.

Aliphatic diisocyanis; ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate , Buten diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-trimethylundecamethylene diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate, 1,8-Diisamethylene-4-isocyanismethyloctane, 2,5,7-trimethyl-1,8-diisocyanis-5-isocyanismethyloctane, bis (isocyanisethyl) carbonate, bis (isocyanisethyl) ether, 1, 4-butylene glyco-ldipropyl ether ω, ω'-diisocyanate, lysine diisocyanate methyl ester

Aromatic diisocyanate; xylylene diisocyanate (o-, m-, p-), tetrachloro-m-xylylene diisocyanate, 4-chlor-m-xylylene diisocyanate, 4,5-dichloro-m-xylylene diisocyanate, 2 , 3, 5, 6-Tetrabrom-p-xylylene diisocyanate, 4-methyl-m-xylylene diisocyanate, 4-ethyl-m-xylylene diisocyanate, bis (isocyanate ethyl) benzene, bis (isocyanatepropyl) benzene, 1, , 3-bis (α, α-dimethylisocyanatemethyl) benzene, 1,4-bis (α, α-dimethylisocyanatemethyl) benzene, α, α, α', α'-tetramethylxylylene diisocyanate, bis (isocyanate) Butyl) benzene, bis (isocyanatemethyl) naphthalin, bis (isocyanatemethyl) diphenyl ether, bis (isocyanate ethyl) phthalate, 2,6-di (isocyanatemethyl) furan, phenylenediisocyanate, tolylene diisocyanate, ethylphenylenedi isocyanate, isopropyl Phenylene diisocyanate, dimethyl phenylenedi isocyanate, diethyl phenylenedi isocyanate, diisopropyl phenylenedi isocyanate, naphthalene diisocyanate, methyl naphthalene diisocyanate, biphenyl diisocyanate, trizine diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate , Bibenzyl-4,4'-diisocyanate, bis (isocyanatephenyl) ethylene, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, phenylisocyanatemethylisocyanate, phenylisocyanate ethyl isocyanate, tetrahydronaphthylene diisocyanate, hexahydrobenzene Diisocyanate, hexahydrodiphenylmethane-4,4'-diisocyanate, diphenylether diisocyanate, ethyleneglycol-diphenylether diisocyanate, 1,3-propylene glycol-diphenylether diisocyanate, benzophenone diisocyanate, diethyleneglycol-diphenylether diisocyanate, dibenzofurandiisocyanate, carbazole diisocyanate, ethyl Carbazole diisocyanate , Dichlorocarbazole diisocyanate

Sulfur-containing aliphatic diisocyanate; thiodiethyldiisocyanate, thiodipropyldiisocyanate, thiodihexyldiisocyanate, dimethylsulfondiisocyanate, dithiodimethyldiisocyanate, dithiodiethyldiisocyanate, 1,2-bis (2-isocyanateethylthio) ethane, 2,4-dithiapentane -1,3-diisocyanate, 2,4,6-trithiaheptane-3,5-diisocyanate, 2,4,7,9-tetrathiapentane-5,6-diisocyanate, bis (isocyanatemethylthio) phenylmethane, bis (Isocyanate Methylthio) methane, bis (isocyanate ethyl thio) methane, bis (isocyanate ethyl thio) ethane, bis (isocyanate methyl thio) ethane, 1,5-isocyanate 2-isocyanate methyl-3-thiapentane

Aliphatic sulfide-based diisocyanates; bis [2- (isocyanatemethylthio) ethyl] sulfide, bis (isocyanatemethyl) sulfide, bis (isocyanate ethyl) sulfide, bis (isocyanatepropyl) sulfide, bis (isocyanatehexyl) sulfide, bis (isocyanatemethyl) ) Disulfide, bis (isocyanate ethyl) disulfide, bis (isocyanate propyl) disulfide

Aromatic sulfide disulfides; diphenylsulfide-2,4'-diisocyanate, diphenylsulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate dibenzylthioether, bis (4-isocyanate methylbenzene) ) Sulfide, 4,4'-methoxybenzenethioethyleneglycol-3,3'-diisulfate, diphenyldisulfide-4,4'-disulfide, 2,2'-dimethyldiphenyldisulfide-5,5'-disulfide, 3 , 3'-dimethyldiphenyl disulfide-5,5'-diisulfate, 3,3'-dimethyldiphenyldisulfide-6,6'-disulfide, 4,4'-dimethyldiphenyldisulfide-5,5'-diisulfate, 3,3 '-Dimethoxydiphenyl disulfide-4,4'-diisulfate, 4,4'-dimethoxydiphenyldisulfide-3,3'-diisulfate

Aliphatic sulfone diisocyanate; bis (isocyanate methyl) sulfone

Aromatic sulfone-based diisulfones; diphenyl sulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benziliden sulfone-4,4'-diisocyanate, diphenylmethanesulfon-4,4'-diisocyanate, 4-methyldiphenylmethane Sulfone-2,4'-diisulfone, 4,4'-dimethoxydiphenylsulfone-3,3'-diisulfone, 3,3'-dimethoxy-4,4'-diisocyanate dibenzyl sulfone, 4,4'-dimethyldiphenyl sulfone -3,3'-diisulfone, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisulfone, 4,4'-dimethoxybenzeneethylenedisulfone-3,3'-diisulfone, 4,4'- Dichlorodiphenyl sulfone-3,3'-diisocyanate

Sulfonate-based diisocyanate; 4-methyl-3-isocyanatebenzenesulfonyl-4'-isocyanatephenol ester, 4-methoxy-3-isocyanatebenzenesulfonyl-4'-isocyanatephenol ester

Aromatic sulfonic acid amide diisocyanate; 4-methyl-3-isocyanatebenzenesulfonylanilide-3'-methyl-4'-isocyanate, dibenzenesulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-dimethoxybenzenesulfonyl -Isocyanate-3,3'-diisocyanate, 4-methyl-3-isocyanate benzenesulfonylanilide-4-methyl-3'-isocyanate

Sulfur-containing heterocyclic diisocyanate; thiophene-2,5-diisocyanate, thiophene-2,5-diisocyanatemethyl, 1,4-dithian-2,5-diisocyanate, 1,4-dithian-2,5-diisocyanatemethyl, 1, 3-Dithiolane-4,5-diisocyanate, 1,3-dithiolane-4,5-diisocyanatemethyl, 1,3-dithiolane-2-methyl-4,5-diisocyanatemethyl, 1,3-dithiolane-2,2- Diisocyanate ethyl, tetrahydrothiophene-2,5-diisocyanate, tetrahydrothiophene-2,5-diisocyanate methyl, tetrahydrothiophene-2,5-diisocyanate ethyl, tetrahydrothiophene-3,4-diisocyanatemethyl, 2- (1,1-diisocyanate) Methyl) thiophene, 3- (1,1-diisocyanate methyl) thiophene, 2- (2-thienylthio) -1,2-diisocyanate propane, 2- (3-thienylthio) -1,2-diisocyanate propane, 3- (2) -Thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (3-thienyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthio) -1,5-diisocyanate- 2,4-dithiapentane, 3- (3-thienylthio) -1,5-diisocyanate-2,4-dithiapentane, 3- (2-thienylthiomethyl) -1,5-diisocyanate-2,4-dithiapentane, 3- (3-Thienylthiomethyl) -1,5-diisocyanate-2,4-dithiapentane, 2,5- (diisocyanatemethyl) thiophene, 2,3- (diisocyanatemethyl) thiophene, 2,4- (diisocyanatemethyl) thiophene, 3,4- (diisocyanate methyl) thiophene, 2,5- (diisocyanatemethylthio) thiophene, 2,3- (diisocyanatemethylthio) thiophene, 2,4- (diisocyanatemethylthio) thiophene, 3,4- (diisocyanatemethylthio) thiophene, 2,4-bisisocyanatemethyl-1,3,5-tritian

The diisocyanate compound is usually used for producing polyurea and polyurethane, but industrially, it is produced by reacting with phosgene using the corresponding diamine as a starting material. That is, it is also possible to produce a desired diisocyanate compound <A> or other diisocyanate compound using the diamine compound <B> as a starting material.

6. Compound having a polymerizable functional group capable of radical curing <E>
The compound <E> having a polymerizable functional group capable of radical curing of the present invention has a terminal group that can be added to the terminal group of the block copolymer (P) of the present invention.
Specific examples of the compound that can be used as the compound <E> having a polymerizable functional group capable of radical curing include the following.

6.1 When the terminal of the (meth) acrylic compound block copolymer (P) having an isocyanate group is -NH ₂ or -OH, the compound having a (meth) acryloyl group has an isocyanate group (-NCO) (-NCO). Meta) Acryloyl compounds can be used.

The (meth) acrylate compound having an isocyanate group is not particularly limited, but for example, as a compound having one acrylic group in the molecule, 2-isocyanatoethyl methacrylate (for example, Showa Denko KK Karens). MOI), 2-isocyanatoethylacrylate (for example, Karenz AOI manufactured by Showa Denko KK), Karenz MOI-EG (manufactured by Showa Denko KK) and the like. Examples of the compound having two acrylic groups in the molecule include 1,1- (bisacryloyloxymethyl) ethyl isocyanate (for example, Calends BEI manufactured by Showa Denko KK).

A general urethanization catalyst such as dibutyltin dilaurate can be used as the reaction catalyst for the reaction between the (meth) acrylic compound containing an isocyanate group and the block copolymer (P) having a —OH group at the end. The urethanization catalyst includes, for example, various nitrogen-containing compounds such as N, N-dimethylaminoethyl ether, triethylamine, triethylenediamine, or N-methylmorpholine, and various types such as potassium acetate, zinc stearate, and tin octylate. Examples thereof include various organic metal compounds such as metal salts and dibutyltin dilaurate.

6.2 When the terminal of the (meth) acrylic compound block copolymer (P) having an amino group, a carboxyl group or a hydroxyl group is -NCO, the compound having a (meth) acryloyl group is a functional group capable of reacting with the terminal isocyanate. As long as it contains the above, there is no particular limitation, and it can be appropriately selected according to the purpose. For example, a (meth) acrylic compound having a hydroxyl group (-OH), a carboxyl group (-COOH), and an amino group (-NH ₂ ) can be used.

6.2.1 (meth) acrylic compound having an amino group The (meth) acrylate compound having an amino group is not particularly limited, but for example, the side chain is a 1-aminoethyl group. Examples thereof include a certain (meth) acrylic acid ester, a (meth) acrylic acid ester having a 1-aminopropyl group as a side chain, and the like.

6.2.2 (Meta) Acrylo Compound Having a Carboxyl Group The (meth) acryloyl compound having the carboxyl group (-COOH) is not particularly limited, but is, for example, 2- (meth) acryloyloxyethyl. Examples thereof include succinate, 2-acryloyloxyethyl-succinic acid, monohydroxyethyl phthalate (meth) acrylate, and the like.

6.2.3 (Meta) acrylic compound having a hydroxyl group The (meth) acrylic compound having a hydroxyl group is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester or an amide compound is preferable and specific. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyethylene glycol diacrylate, polypropylene glycol mono (meth). ) Acrylate, Tris (hydroxyethyl) isocyanuric acid di (meth) acrylate, pentaerythritol tri (meth) acrylate, hydroxyethyl acrylamide, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate , Neopentyl glycol mono (meth) acrylate, trimethyl propandi (meth) acrylate, and the like.

7. Reaction solvent The copolymer used in producing the copolymer 1, the copolymer 2, the block copolymer (P), and the reactive block copolymer (Q) of the present invention is such a copolymer. It is not particularly limited as long as it can be synthesized. Examples of the reaction solvent include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and methyl 3-methoxypropionate. Ethyl 3-ethoxypropionate, cyclohexanone, 1,3-dioxolane, ethylene glycol dimethyl ether, 1,4-dioxane, propylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, anisole, ethyl lactate, Diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, diethylene glycol isopropylmethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, ethylene glycol monophenyl. Ether, triethylene glycol monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monobutyl ether (1-butoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monomethyl ether (1-methoxy-) 2-propanol), triethylene glycol divinyl ether, tripropylene glycol monomethyl ether, tetramethylene glycol monovinyl ether, methyl benzoate, ethyl benzoate, 1-vinyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-ethyl -2-pyrrolidone, 1- (2-hydroxyethyl) -2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethyl Formamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methyl-ε-caprolactam, 1,3-dimethi Lu-2-imidazolidinone, γ-butyrolactone, 4-methyl-2-pentanone, methyl ethyl ketone, acetone, toluene, tetrahydrofuran, ethyl lactate, 3-methoxy N, N-dimethylpropanamide, isopropyl alcohol, normal butyl alcohol and normal Propyl alcohol can be mentioned.

Among these, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, and 4-methyl-2-pentanone are used as polyurea-based alternating copolymers. And the polyurethane-based copolymer has good solubility and the polymerization proceeds uniformly, which is preferable.
Only one kind of these reaction solvents may be used, or two or more kinds may be mixed and used. Further, other solvents other than the above reaction solvent can be mixed and used.

It is preferable to use 100 parts by weight or more of the reaction solvent with respect to 100 parts by weight of the total of the diisocyanate compound <A> and the diamine compound <B> because the reaction proceeds smoothly. The reaction is preferably carried out at 0 ° C. to 150 ° C. for 0.2 to 20 hours.

8. Applications of Polyurea-based Alternate Copolymer The polyurea-based alternating copolymer of the present invention is utilized as a material for protecting an image display element from impact in the field of image display elements represented by liquid crystal displays and organic EL displays. be able to. For example, in a liquid crystal display, it may be used as a film or coating material to be installed on the front surface or back surface of a cover glass or cover film, or on the front surface or back surface of a polarizing plate. Organic EL displays are becoming thinner and lighter due to their flexibility, and the need for protecting elements from external forces such as impacts is becoming extremely high. Along with this, the polyurea-based alternating copolymer of the present invention is useful as a back film or a coating material to be installed on the front surface or back surface of a cover glass or cover film, the front surface or back surface of a polarizing plate, or the element body. It can also be used as a material inside an element such as a fill material, a sealing material, a dam material, a buffer material, and a flattening film.

In the field of automobiles, it is also useful as a material for protecting the exterior and interior of automobiles from impacts. For example, the external coating may be used as a paint protection film or a coating material for protecting scratches from flying stones and the like. Taking advantage of the excellent impact resistance of polyurea-based alternating copolymers, it may be used as a film or coating material to be installed in interlayer films, glazing, rear windows, rear-view mirrors, sensors, etc. of laminated glass for automobiles.

Polyurea and polyurethane-based materials also have the potential to be used as biocompatible materials. Expected to be applied to medical devices that require blood compatibility, such as filtering by spinning such as electrospinning to form dialysis membranes, hollow fibers such as artificial cardiopulmonary, and coating on needles for infusion that are embedded in the body for a long time. can.

In the field of building materials, it may be used as a film or coating material for the purpose of preventing the scattering of windowpanes, for example, to prevent the windowpanes of high-rise buildings from being destroyed, scattered and falling in the event of an earthquake or earthquake. It may be used to prevent the glass from breaking. Polyurea is known to enhance impact resistance by coating structural buildings, such as concrete and block walls, and can also be used as a coating material to prevent collapse of structural buildings in the event of terrorism, earthquakes, or earthquakes. good.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
The meanings of the symbols used in the examples are as follows.
PSt: Polystyrene BAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] Propane DMAc: N, N-dimethylacetamide THF: tetrahydrofuran DMF: N, N-dimethylformamide HXDI: 1,3-bis (isocyanate) Natomethyl) cyclohexane MEHQ: 4-methoxyphenol MEOH: methanol BEI: 1,1- (bisacryloyloxymethyl) ethyl isocyanate (Karenzu BEI manufactured by Showa Denko KK)
AOI: 2-Isocyanatoethylacryllate (Karenzu AOI manufactured by Showa Denko KK)

Next, the analysis conditions in the production example and the example are shown.
<GPC>
Equipment: LC-2000Plus series manufactured by JASCO Corporation (detector: differential refractometer)
Solvent: THF / DMF = 1/1 (v / v)
Flow velocity: 0.5 ml / min
Column temperature: 40 ° C
Column used: Showa Denko Corporation, Asahipak GF-1G 7B (guard column) + Asahipak GF-7M HQ, exclusion limit molecular weight (PEG) = 10,000,000)
Standard sample for calibration curve: Pst (PSS Polymer Standards Service)

<Dynamic viscoelasticity measurement>
Equipment: RSA-G2 manufactured by TA Instruments
Measurement temperature: -30 ° C to 200 ° C
Frequency: 1Hz
Glass transition temperature (Tg): Peak temperature elastic modulus of Tanδ: Value of storage elastic modulus at 50 ° C.

[Production Example 1] Synthesis of Alternate Copolymer (1) Under a nitrogen atmosphere, BAPP (manufactured by Wakayama Seika Kogyo Co., Ltd.) 14.3 g in a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. , DMAc (57.4 g, manufactured by Kanto Chemical Co., Ltd., dehydrated) was introduced. It was heated to 120 ° C. using an oil bath. Next, a solution in which HXDI (5.66 g, manufactured by Mitsui Chemicals, Inc., product name; Takenate 600) was dissolved in DMAc (22.6 g, manufactured by Kanto Chemical Co., Ltd., dehydrated) was collectively introduced with a syringe. The reaction was initiated (HXDI: BAPP = 1.0: 1.2, molar ratio). Then, the mixture was stirred for 6 hours while being maintained at 120 ° C. to obtain a transparent reaction solution. The weight average molecular weight determined by GPC analysis of the reaction solution was 8,200, and the molecular weight distribution was 2.7.
Further, prepare 600 mL of Solmix AP-1 (manufactured by Japan Alcohol Trading Co., Ltd .: ethanol, 2-propanol, methanol, water mixture) in a 1 L beaker, and while stirring with a stirrer, use a pass tool to add 20 mL of the obtained polymer solution. Dropped slowly. White solids were deposited in the solution. After collecting the precipitate by suction filtration, it was dried in a vacuum dryer set at 120 ° C. for 6 hours to obtain a pale red alternating copolymer (1).

[Production Example 2] Synthesis of Alternate Copolymer (2-2) Under a nitrogen atmosphere, HXDI (51.1 g, manufactured by Mitsui Kagaku Co., Ltd.) was placed in a 1000 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. Product name; Takenate 600), DMAc (249.0 g, manufactured by Kanto Kagaku Co., Ltd., dehydrated) was introduced. A solution prepared by immersing the flask in a water bath and dissolving the hydroxyl-modified silicon compound at both ends (198.8 g, manufactured by JNC Co., Ltd., trade name: Silaplane FM4411, hydroxyl group equivalent: 564 g / mol) while maintaining the cooling state. The reaction was started by dropping using a dropping funnel (HXDI: FM4411 = 1.5: 1, molar ratio). After that, the reaction was continued for 6 hours to obtain an alternating copolymer (2-2). The obtained reaction solution was transparent, and the weight average molecular weight determined by GPC analysis of the reaction solution was 6100, and the molecular weight distribution was 1.9.

[Production Example 3] Synthesis of Alternate Copolymer (2-1) Under a nitrogen atmosphere, HXDI (4.26 g, manufactured by Mitsui Kagaku Co., Ltd.) was placed in a 200 mL three-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel. Product name; Takenate 600), DMAc (57.6 g, manufactured by Kanto Kagaku Co., Ltd., dehydrated) was introduced. Then, it was heated at 40 ° C. using an oil bath. Add DMAc (14.4 g, manufactured by Kanto Chemical Co., Ltd., dehydrated) to α, ω- (3-aminopropyl) polydimethylsiloxane (13.74 g, manufactured by JNC Co., Ltd., trade name: FM3311) and dissolve. The solution was dropped and the reaction was started. Then, the mixture was stirred at the same temperature for 5 hours to obtain an alternating copolymer (2-1). The obtained reaction solution was transparent, and the weight average molecular weight determined by GPC analysis of the reaction solution was 9,900, and the molecular weight distribution was 3.2.

[Production Example 4] Synthesis of Block Copolymer (P) (1) The copolymer weight obtained in [Production Example 1] was placed in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. The coalescence (1) (5.01 g) was introduced, and then DMAc (20.0 g, manufactured by Kanto Kagaku Co., Ltd., dehydrated) was added. After heating to 120 ° C. using an oil bath, the copolymer (2-2) (30.0 g) obtained in [Production Example 2] and DMAc (45.1 g) were introduced into the dropping funnel. (Copolymer concentration: 20%). After that, dropping was started promptly, and the copolymer (1) and the copolymer (2-2) were uniformly mixed in the flask while stirring (copolymer (1): copolymer (2-2). ) = 1: 3, weight ratio). The block copolymer (P) (1) was obtained by subjecting to stirring at the same temperature for 6 hours. The obtained reaction solution was transparent, and the weight average molecular weight determined by GPC analysis was 54,200, and the molecular weight distribution was 5.8.

[Production Example 5] Synthesis of Block Copolymer (P) (2) A copolymer obtained in [Production Example 3] in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. The polymer (2-1) (75.0 g) was introduced. Then, it was heated to 120 ° C. using an oil bath. A solution in which 5.00 g of the copolymer (1) obtained in [Production Example 1] and DMAc (20.0 g) were mixed was introduced into the dropping funnel (copolymer concentration: 20%). After that, dropping was started promptly, and the copolymer (1) and the copolymer (2-1) were uniformly mixed in the flask while stirring (copolymer (1): copolymer (2-1). ) = 1: 3, weight ratio). The block copolymer (P) (2) was obtained by subjecting to stirring at the same temperature for 6 hours. The obtained reaction solution was transparent, and the weight average molecular weight determined by GPC analysis was 69,700, and the molecular weight distribution was 9.9.

[Example 1] The reactive block copolymer (Q) (1) was obtained in [Production Example 4] in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a synthetic nitrogen atmosphere. After heating the copolymer (1) to 80 ° C., BEI (1.764 g, manufactured by Showa Denko KK, product name; Karenz BEI) and MEHQ (0.020 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) Was introduced into the dropping funnel and immediately dropped, and the reaction was started. Then, the mixture was stirred at the same temperature for 5 hours to obtain a transparent reaction solution. Then, AOI (0.585 g, manufactured by Showa Denko KK, product name; Calends AOI) was introduced into the dropping funnel, and the reaction was promptly started by dropping. Then, the flask was subjected to stirring at the same temperature for 5 hours, and then the flask was cooled to room temperature by bathing up. MEOH (0.8955 g, manufactured by Kanto Chemical Co., Inc.) was added and stirred for 30 minutes to obtain a UV-curable reactive block copolymer (Q) (1). The obtained reaction solution was transparent, and the weight molecular weight determined by GPC analysis was 55,000, and the molecular weight distribution was 5.4.

[Example 2] Synthesis of reactive block copolymer (Q) (2) Obtained in [Production Example 5] in a three-necked flask (200 mL) equipped with a reflux condenser, a thermometer and a dropping funnel under a nitrogen atmosphere. After heating the copolymer (2) to 80 ° C., BEI (1.372 g, manufactured by Showa Denko KK, product name; Karenz BEI) and MEHQ (0.020 g, manufactured by Tokyo Kasei Kogyo Co., Ltd.) Was introduced into the dropping funnel and rapidly dropped to start the reaction. Then, the mixture was stirred at the same temperature for 5 hours to obtain a transparent reaction solution. Then, AOI (0.584 g, manufactured by Showa Denko KK, product name; Calends AOI) was introduced into the dropping funnel, and the reaction was promptly dropped to start the reaction. Then, the flask was subjected to stirring at the same temperature for 5 hours, and then the flask was cooled to room temperature by bathing up. MEOH (0.7066 g, manufactured by Kanto Chemical Co., Inc.) was added and stirred for 30 minutes to obtain a UV-curable reactive block copolymer (Q) (2). The obtained reaction solution was transparent, and the weight molecular weight determined by GPC analysis was 53,000, and the molecular weight distribution was 7.1.

[Example 3] Preparation of UV cured film (1) Irgacure 127 (BASF Japan Ltd.) was added to 20 g of the reaction solution of the reactive block copolymer (Q) (2) obtained in [Example 2] as a curing agent. ) Was dissolved in 0.08 g to adjust the coating agent (1) (solid content concentration 19 wt%). The solubility was good.
As a release film, NSD-100 (PET base material, manufactured by Fujimori Kogyo Co., Ltd.) was used. Using the coating agent (2), coat the release film with a bar coater RD65 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) so that the dry film becomes 10 μm, and dry at 120 ° C. for 3 minutes. Subsequently, the coating film was photo-cured under a light irradiation condition of 1000 mJ / cm ² using a high-pressure mercury lamp to form a transparent UV-cured film (1). The obtained UV cured film (1) was peeled off from the release film to obtain a transparent self-supporting film.

[Example 4] Preparation of UV-cured film (2) Irgacure 127 (BASF Japan Ltd.) was added to 20 g of the reaction solution of the reactive block copolymer (Q) (2) obtained in [Example 2] as a curing agent. ) Was dissolved in 0.08 g to adjust the coating agent (1) (solid content concentration 19 wt%). The solubility was good.
As a release film, NSD-100 (PET base material, manufactured by Fujimori Kogyo Co., Ltd.) was used. Using the coating agent (2), coat the release film with a bar coater RD65 (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) so that the dry film becomes 10 μm, and dry at 120 ° C. for 3 minutes. Subsequently, the coating film was photo-cured under a light irradiation condition of 1000 mJ / cm ² using a high-pressure mercury lamp to form a transparent UV-cured film (1). The obtained UV cured film (2) was peeled off from the release film to obtain a transparent self-supporting film. When the reactive block copolymer (Q) (2) is used, it can be peeled off from the release film even before UV curing (after drying at 120 ° C. for 3 minutes) to become transparent and self-supporting. A film was obtained.

Test of cured film (1) Evaluation of film-forming property In Examples 3 to 4, it was evaluated by ◯ and × whether or not it could be peeled off as a self-standing film from the release film. Moreover, the appearance of the cured film was visually evaluated.
(2) Dynamic Viscoelasticity Measurement The obtained cured film (2) and UV cured film (1) and (2) were subjected to dynamic viscoelasticity measurement, and the glass transition temperature (Tg) and elastic modulus were evaluated. ..
(3) Bending characteristics The obtained cured films (2) and UV cured films (1) and (2) were subjected to a 180 ° bending test (500 g load) to confirm the presence or absence of fracture.

The results of the above (1), (2) and (3) are shown in Table 1.

As is clear from the above results, the UV-curable reactive block copolymers (Q) of Examples 1 and 2 have excellent solubility in organic solvents. Further, as is clear from the results in Table 1, in Examples 3 to 4, the UV-curable block copolymer (Q) can be UV-curable and has excellent film-forming properties. Further, the obtained UV cured film is excellent in transparency, heat resistance and flexibility.

From the above, the reactive block copolymer (Q) of the present invention is soluble in a general-purpose organic solvent and has (meth) acrylate groups at both ends. A cured film can be easily obtained by irradiation with an electron beam. The obtained cured film is excellent in transparency, heat resistance, and flexibility, and is extremely useful as a coating material or a base resin for a film base material.

Claims (8)

It contains a repeating unit represented by the formula (3), which is a double addition copolymer of the following alternate copolymer 1 and the following alternate copolymer 2, has a weight average molecular weight of 5,000 to 1,000,000, and has a terminal. At both ends of the block copolymer (P), which is either -NH ₂ , -OH or -NCO,
A compound <E> having a (meth) acryloyl group as a polymerizable functional group having a group that can be added to both terminal groups of the block copolymer (P) and capable of radical curing by irradiation with active energy rays is added. Reactive block copolymer.
-[(Alternate copolymer 1)-(Alternate copolymer 2)-]-Formula (3)
Alternating copolymer 1:
It is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <B>, and is of the formula (1).
-[(A)-(B)-]-Equation (1)
Polyurea-based alternating copolymer containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NH ₂ or -NCO at both ends;
Alternating copolymer 2:
It is a double-addition copolymer of the diisocyanate compound <A> and the diamine compound <C ¹ >, and is of the formula (2-1).
-[(A)-(C ¹ )-]-Equation (2-1)
Polyurea-based alternating copolymer 2-1 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -NH ₂ at both ends.
And a polyaddition copolymer of the diisocyanate compound <A> and the diol compound <C ² >, of the formula (2-2).
-[(A)-(C ² )-]-Equation (2-2)
Polyurethane-based alternating copolymer 2-2 containing a repeating unit represented by, having a weight average molecular weight of 5 to 300,000, and having -NCO or -OH at both ends.
At least one alternating copolymer selected from;
(In the formula (A), at least one of the aliphatic isocyanate structural units having an independent cyclic structure in the molecule;
(B) is at least one structural unit independently selected from an aromatic diamine, an aromatic diamine having an ether bond, and an aliphatic diamine having a cyclic skeleton;
(C ¹ ) is at least one structural unit selected from a linear aliphatic diamine, an aliphatic diamine having an ether bond, and a diamine having a siloxane skeleton;
(C ² ) represents at least one structural unit selected from a linear aliphatic diol, an aliphatic diol having an ether bond, and a diol having a siloxane skeleton.
However, when both ends of the alternate copolymer 1 are -NCO, both ends of the alternate copolymer 2 are -NH ₂ or -OH;
When both ends of the alternate copolymer 1 are -NH ₂ , both ends of the alternate copolymer 2 are -NCO. ) Both ends of the block copolymer (P) are independently -NH ₂ or -OH;
The group that can be added to both terminal groups of the block copolymer (P) of compound <E> is -NCO, and the polymerizable functional group that can be radically cured by irradiation with active energy rays is a (meth) acryloyl group. The reactive block copolymer according to claim 1, wherein the reactive block copolymer is. Both ends of the block copolymer (P) are -NCO;
The groups that can be added to both terminal groups of the block copolymer (P) of compound <E> are -NH ₂ groups, -COOH or -OH, and radical curing by irradiation with active energy rays is possible. The reactive block copolymer according to claim 1, wherein the polymerizable functional group is a (meth) acryloyl group. The reactive block copolymer according to any one of claims 1 to 3 , wherein both ends of the alternate copolymer 1 are -NCO and both ends of the alternate copolymer 2 are -NH ₂ or -OH. Combined. The reactive block copolymer according to any one of claims 1 to 3 , wherein both ends of the alternate copolymer 1 are -NH ₂ and both ends of the alternate copolymer 2 are -NCO. The reactive block copolymer according to any one of claims 1 to 5 , wherein the alternate copolymer 2 is a polyurea-based alternate copolymer 2-1. The reactive block copolymer according to any one of claims 1 to 5 , wherein the alternate copolymer 2 is a polyurethane-based alternate copolymer 2-2. The diisocyanate compound <A> is a compound represented by the following formulas (I) to (X).
In the following formulas (I) to (X), R ₁ , R ₂ , R ₃ and R ₄ are independently hydrogen or linear or branched alkyl having 1 to 7 carbon atoms.
X is an independently linear or branched alkylene having 1 to 7 carbon atoms.
Y is independently oxygen, sulfur, a linear or branched alkylene with 1-7 carbon atoms, -C (CF ₃ ) _2- or -SO _2- , respectively.
The reactive block copolymer according to any one of claims 1 to 7 .